Ornamentation



ENTORS R. E. T. HAFF ET AL ORNAMENTATION Filed Oct. ll, 1941 Oct. 19, 1943.

Patented Oct. 19, 1943 UNITED STATE s 'PATENT oFFicE- ortNAMENTATIoN Raymond E. T.v` Hai, Greeneville, Del., and John Conlyn Creadick and Thomas F. Bani'gan, Kenf more, N. Y., assignors to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware Application October 111, 1941, Serial No. 414,590

8 Claims. (Cl. 41-17) l `has not been offered to the public or described in the literature. A demand for sucha product has long existed, and much time and effort has ing layer effectively simulates a metallic gold appearance.

Custom has long required thathottles of many types of alcoholic liquors, particularly wines,

have the upper part of the neck, and the closure,

encased in a very thin metal capsule or a wrapping of metal foil. This practice has also been adopted for a great deal of the bottled non-alcoholic beverages for the primary purpose ofsales appeal. This type (metal foil) of secondary closure has many disadvantages, inter alia,`poor iit resulting in an unattractive appearance, lack of adhesion which allows it to slip off the bottle neck before the time of wilful removal, and com plete opaqueness requiring that sections be cut out if visual inspection of the underlying material is to be made. Y

Shrinkable, tube-shaped, regenerated cellulose bands have been used as secondary closures` for hotties for some years, because they act effectively to secure easily displaceable primary closures, as deterrents against tampering, aid in positioningrevenue stamps, etc. (see U. S. A. Patent No. 1,647,489 to Webster). Since these bands can be colored and printed upon, they may contribute to the decorative appearance of the unit.

To seal and/or" decorate a bottle, the shrinkable band in gel (hydrated) form is placed over the bottle top (the primary closure, such as stopper or screw cap, being in place) and allowed y to dry. The water evaporating from the band causes it to shrink and iit into very rm engagement with the underlying structure.

The conventional details of band manufacture are disclosed in U. S. A. Patent No. 2,161,561 (and 1,647,489) to Dalton, and since the processing is analogous to that employed with cellulosic sheet (see U. S. A. Patents No. 1,548,864, 1,601,289, and 2,123,883), reference is made to such prior art for conventional details in the interest of brevity.

It is known that such'bands can be rendered more attractive by pigmentation, printing, dyeing, etc. (see U. S. A. Patents No. 1,997,769 to Fletcher, 2,071,024 to Clark, and 2,141,744 to Evans), as previously indicated, but up to the present time a. band having a truly metallic appearance regardless of the use to which it is put,

been spent in research on this problem.

' The production of a regenerated cellulosic band having the appearance of gold foil, was the primary object of this invention. Another object was to develop a non-brous band having clear andl gold sections. Still other'ob-jectswere to improve thevphysical characteristics of kshrink-- able cellulosic bands, to produce cellulosic sheet material having a more metallic appearance than heretofore possible, and to produce by pigmenting and dyeing, cellulosic pellicles simulating thin metal sheet. A general advance in theart, and other objects which will appear hereinafter,

are also contemplated.

Vsurface presented to the eye) `containing about 45% thin, iiat, ground mical particles, and an inner layer containing about 12% titanium dioxide pigment, these proportions beingbased on the cellulose present, provide the aforementioned characteristic.

How the foregoing objects and related'` ends are accomplished will'fbe apparent from the following exposition, in which are disclosed the principle and divers embodiments of the invention, including the best mode contemplated for carrying out the same. The written description is amplified by the accompanying drawing, in which:

Figure 1 is an elevation view of a gel regenerated cellulose band of this invention;

Figure 2 is a perspective view of a section of tubing similar to that shown in Figure 1,.but on a larger scale and with the parts broken away; Figure 3 is a fragmentary perspective view of the portion, indicated atJ, of the -band shown in Figure 2 but greatly enlarged to show the relation of the colored parts at their juncture; Figure 4 is an end or plan view of a tube such as that from which the flattened section shown in Figure 2 wouldbe cut;

Figure 5- is a perspective view of a bottle top and its primary closure, having the gel secondaryclosure of Figure 1 in position for Vdrying thereon; i

Figure 6 is a perspective view of av bottle top equal thiclmess.

gerated for purposes of clarity in i1lustration',`a` gel regenerated cellulose band is indicated at il in Figures 1, 2 and 5,'and a tube, of which said band would be a section, is shown at i in Figurea.

The band in Figure 2 is shown withy a party broken away, to better illustrate its' construction. It has narrow, clear or transparent lside portions indicated at I2, and opaque gold front and rear portions at I3. opaque white portions il.

In Figures 5 and 6, 2li indicates the neckv of av bottle closed with a primaryclosure 2i,` and sealed witha revenue stamp 22. In conventional practice the transparent sectionl i2 ofthefgel band is positioned' overthe revenue stamp, as

` shown in Figure 5,-v so that when the band dries the printing on the stamp is legiblebu't` completely covered and held tightly `againstthe bottle neck. asshown in Figure 6.

The `mechanical steps involved ,in producing these bands are generally conventionalbeing disclosed in U. S. A. Patent No. 2,14:1,'If16V td Vautier l: Iiiiys.` 'I'hey involve squirting concentric layers of viscose, contacting 'the squirted` layers, and treating the resulting structure with a coagulating bath immediately after the layers are joined*` but before substantial diffusion of the different types of viscose can take place. One very satisfactory extruding'scheme is illustrated in Figure '1, in which clear viscoselayers `are indicated at 12, opaque white layers at 14, and layers contain. ingv mica and yellow pigment, or equivalent color,- ing agent, at 13. `Other acceptable arrangements are shown in Figures 8 and 9,. wherein the numerals l2 and 82 indicate clearlayers, 83 and 93 indicate themica-containing layers, .and 84 and Il indicate the opaque titanium dioxide-containing layers. i i l j,

`Ordinarily theinner and outerlayers are of Surface tension causes the nn'. ished bands to be in the same general arrangement, for example, that shown lin Figure 4,

whether or not the clear sections (12, 82 and 92)l are equal or only half as thick as the opaque sections (1H-1513+ and 934-941). A

The thicknesslof the gel band may be varied to suit individual requirements, but ordinarily a thickness of 0.017 inch, which gives a thickness of approximately 0.004 to 0.005 inch in the dry state, is employed. In allcases the White pigmented under layer` must be thick enough to give opacity, for example 0.006to 0.012, preferably 0.008` to 0.01 inch, and the outer mica layer must be thick enough to give, in cooperation with the other features, the desired `'metallic effect, preferably 0.008 to 0.01 inch,

Considerations `of rstrength and shrinkage characteristics generally control the dimensions.

been obtained when the titamica-containing layers were not of the same thickness, .but it is preferred that the thickness of each layer be within the range of the total thickness of the band. layer contains 4.5%v mica Good results have nium dioxide and Preferablythe outer (based on the cellulose present), but satisfactory results can be obtainedwith proportions in the range 30% to 60%, The amount of titanium dioxide contained in the opaque layer is 12% to 16%, preferably 12%, of Ithe cellulosic material present in that layer.

Bands having a satisfactory gold appearance have been obtained by incorporating nely ground unreduced yellow vat dyes singly and in mixtures, within the mica layer. Preferably 1-(1':9' isothiazolanthr'one 2 carbonyl) 6 anthrone-2-carbonyl) -amino--benzoyl-aminoanthraquinone are utilized for this purpose. The amount ofthe dye pigment so employed is preferably 6%. but acceptable results are Inside the gold. portions kare A Patent 321,183). vThe corresponding yellow sulobtained with 2% to 10% (based on' the cellulose). Equal or superior gold appearances are obtained bydyeing the gel regenerated cellulose productwith one or more yellow sulfur dyes. A particularly useful dye, for this purpose, is the thionation product of a mixture of metatoluylene-diamine and benzidine (see French furdye from paratoluidine and benzidine (C. I. 955) is also quite satisfactory. A band may be both dyed and pigmented, if desired.

The present invention contemplates primarily aV gold band, but it comprehends elements which can be advantageously applied with bands of Vother colors, for example, silver appearing bands, superior to bands previously designed to simulate silver, may be produced by replacing the aforementioned yellow coloring matter with 0.1% to `0.5% of a blackpigment such as colloidal graphite, carbon black, black vat dyes, and the like.

Pr-ferably the size of the mica particles is within the range 20 to 150 microns (measured in the longest dimension), but this range is not absolutely critical and the size may extend somewhat both above and below this range. Wet ground mica gives the most desirable results.

Preferably the size of the titanium dioxide pig- .,.ment particles `is within the range 0.5 to 2 `viscose layer containing the mica, the tube, or the band after being cut therefrom, may be dyed in the conventional way. In such instances the clear window and the opaque layer will be colored.

The transparent section of the band may be omitted, if desired, in which case the tube would vconsist of uniform concentric layers, the outer of which contains the mica and yellow coloring matter, and the inner the titanium dioxide.

The bands may be formed of materials other than regenerated cellulose. for example, cellulose ethers and like materials, coasulable from aqueous or aqueous alkaline solutions. While the non-fibrous cellulosie pellicles are the most common type, in some instances pellicular bands formed rof non-cellulosic materials such as gelatin,`casein and the like, may be used.

The'bands may be perforated to facilitate removal, as pointed out in U. S. A. patent application'Serial No. 327,406, filed April 2, 1940, by Edwards 8:; Mueller. Reference to that application is made for further details in this art.

There are numerous unexpected advantages in 'the present invention, for example, the strength `of the gel band is 20% greater, and the strength of the dried band is 50% greater than a band consisting of a single layer having mica throughoutL Improvements in shrinkage are allo ob.

t invention, the disadvantage of metal secondary closures which cannot provide a window. and heretofore known shrinkable closures which did not have -a metallic look, are overcome. As a result, the bands have a wider appeal, since they furnish the esthetic eiect demanded by customers, and the much desired utilitarian features such as transparent windows, tig-ht nt, etc.

As many apparently widely diierent embodiments of this invention may be made without departing from the spirit and scope thereof, it is tobe understood that this invention is not limited to the specific embodiments thereof except as defined in the appended claims. I

We claim:

1. A shrinkable, cellulosic band secondary closure comprising essentially an outer metallic-appearance portion containing mica and coloring material and an underlying inner opaque portion containing a white pigment.

2. A shrinkable, cellulosic band secondary closure comprising essentially an outer metallicappearing portion containing mica. and coloring agent, and an underlying inner opaque portion containing titanium dioxide pigment.

3. A shrinkable, cellulosic band secondary closur'e comprising essentially an outer metallicappearing portion containing 30%-60% mica and coloring substance, and an underlying inner opaque portion containing 12%-16% titanium dioxide pigment.

sure comprising essentially an outer metallicappearance portion vcontaining 30%-60% mica and yellow vat dye, and an underlying inner opaque portion containing 12%-16% titanium dioxide pigment.

5. A shrinkable, regenerated cellulose band secondary closure of gold appearance, comprising essentially an outer metallic-appearance portion containing about mica particles within the range 20 to 150 microns (measured in the longest dimension) dyed with the yellow sulfur dye obtained by thionating a mixture of metatoluylene-diamine and benzidine, and an underlying inner opaque portion containing about 12% titanium dioxidepigment having a particle size of 0.5 to 2 microns.

6. A regenerated cellulose secondary band closure for bottles and the like, comprising a white 4. A shrinkable, cellulosic band secondary clo- 

